JP7417665B2 - Antiviral aerosol compositions, coatings, and articles - Google Patents

Description

The present invention relates to antiviral aerosol compositions, coatings, and articles.

It is well known that in recent years, with the emergence of new types of influenza viruses and coronaviruses that cause serious symptoms when infected, there has been increasing interest in antiviral agents to prevent viral infections. Based on their structure, viruses are broadly divided into viruses that have an envelope made of lipids and glycoproteins (enveloped viruses) and viruses that do not (non-enveloped viruses). Influenza virus is a typical example of an enveloped virus, and norovirus is a typical example of a non-enveloped virus, but non-enveloped viruses are said to be more resistant to alcohol and heat and more infectious than enveloped viruses. . Therefore, research and development of antiviral agents that exhibit excellent antiviral effects not only against enveloped viruses but also against non-enveloped viruses is being actively conducted, and the present inventors also reported in Patent Document 1 proposed an inorganic antiviral agent made of copper-doped silica as an antiviral agent that exhibits excellent antiviral effects not only against enveloped viruses but also against nonenveloped viruses.

The inorganic antiviral agent proposed by the present inventors in Patent Document 1 can be used as a material to impart antiviral properties to various items around us. When adopting an embodiment in which the silica doped with copper is blended into an aerosol composition and applied to the surface of the article by aerosol, the coating film formed from the aerosol composition containing the silica doped with copper is Aerosol compositions containing copper-doped silica must exhibit excellent antiviral properties and be firmly retained on the surface of articles, and must also have high stability. It must be possible to apply aerosol without causing nozzle clogging.

Japanese Patent Application Publication No. 2021-175741

Therefore, the present invention has developed copper-doped silica that exhibits excellent antiviral properties and has high stability that can form a coating film that is firmly retained on the surface of articles, and that prevents nozzle clogging. It is an object of the present invention to provide an antiviral aerosol composition that can be applied by aerosol without causing such problems, a coating film formed from the antiviral aerosol composition, and an article having the coating film.

As a result of intensive studies in view of the above points, the present inventors have found that when producing an aerosol composition containing copper-doped silica, a polymer containing a vinylpyrrolidone unit as a resin component (film forming agent) is used. We have discovered that by using a combination of copper-doped silica, the coating film formed from the aerosol composition exhibits excellent antiviral properties and is firmly retained on the surface of the article. found that the aerosol composition has high stability and can be applied by aerosol without causing nozzle clogging.

The antiviral aerosol composition of the present invention, which was made based on the above findings, has the following features:
(1) Silica doped with copper; (2) a copolymer of vinylpyrrolidone and vinyl acetate as a polymer containing vinylpyrrolidone units (ratio of vinylpyrrolidone to vinylacetate is 2:8 to 8:2); and At least one member selected from the group consisting of polyvinylpyrrolidone
(3) an alcoholic solvent or a mixed solvent of an alcoholic solvent and water; and (4) a propellant.
Furthermore, in the antiviral aerosol composition according to claim 2, in the antiviral aerosol composition according to claim 1, the silica is further doped with aluminum.
Further, in the antiviral aerosol composition according to claim 3, in the antiviral aerosol composition according to claim 1, the silica is porous silica .
Further , the antiviral aerosol composition according to claim 4 is the antiviral aerosol composition according to claim 1, wherein the weight average molecular weight of the polymer containing the pyrrolidone unit is 5,000 to 1,500, It is 000.
Further, in the antiviral aerosol composition according to claim 5 , in the antiviral aerosol composition according to claim 1, the alcohol solvent is ethanol.
The antiviral aerosol composition according to claim 6 is the antiviral aerosol composition according to claim 1, wherein the propellant is liquefied petroleum gas, nitrogen gas, carbon dioxide, dimethyl ether, hydrofluoroolefin, hydrofluorocarbon. At least one type selected from the group consisting of.
In addition, the antiviral aerosol composition according to claim 7 is the antiviral aerosol composition according to claim 1, wherein the antiviral aerosol composition includes copper-doped silica and a polymer containing a vinylpyrrolidone unit. Coalescence, alcoholic solvent or mixed solvent of alcoholic solvent and water, propellant content is 0.1 to 5wt% of copper-doped silica, and content of polymer containing vinylpyrrolidone units is 0.1 to 5wt%. The content of alcohol solvent or a mixed solvent of alcohol solvent and water is 30 to 90 wt%, and the content of propellant is 5 to 65 wt%.
Further, the antiviral aerosol composition according to claim 8 is the antiviral aerosol composition according to claim 1, wherein the weight ratio of the copper-doped silica and the polymer containing vinylpyrrolidone units (copper-doped silica:polymer containing vinylpyrrolidone units) is 5:95 to 75:25.
Furthermore, the method for producing the antiviral aerosol composition of the present invention includes, as described in claim 9 ,
(1) Silica doped with copper; (2) a copolymer of vinylpyrrolidone and vinyl acetate as a polymer containing vinylpyrrolidone units (ratio of vinylpyrrolidone to vinylacetate is 2:8 to 8:2); and At least one member selected from the group consisting of polyvinylpyrrolidone
(3) A step of mixing an alcohol-based solvent or a mixed solvent of an alcohol-based solvent and water in a processing container and a step of ball milling the stock solution obtained by the preparation method with (4) a propellant. It becomes.
Further, the coating film of the present invention is formed from the antiviral aerosol composition according to claim 1, as described in claim 10 .
Moreover, the article of the present invention has the coating film according to claim 10 , as described in claim 11 .

According to the present invention, copper-doped silica exhibits excellent antiviral properties and has high stability that can form a coating film that is firmly retained on the surface of an article. It is possible to provide an antiviral aerosol composition that can be applied by aerosol without causing clogging, a coating film formed from the antiviral aerosol composition, and an article having the coating film.

The antiviral aerosol composition of the present invention includes:
It comprises (1) silica doped with copper, (2) a polymer containing vinylpyrrolidone units, (3) an alcoholic solvent or a mixed solvent of an alcoholic solvent and water, and (4) a propellant.

In the antiviral aerosol composition of the present invention, the copper-doped silica may be, for example, the inorganic antiviral agent described in Patent Document 1. Here, "copper-doped silica" means silica in which copper is chemically bonded and incorporated into an inorganic network consisting of siloxane bonds constituting the silica. Silica doped with copper may be porous or non-porous, and its shape is not particularly limited.

Copper-doped silica may be further doped with metals such as aluminum, zirconium, cobalt, manganese, iron, and the like.

The content of copper in the copper-doped silica (or the total amount of each when using a combination of other metals in addition to copper) is, for example, 0.01 to 40 wt%, preferably 0.1 to 20 wt%, or more. Preferably it is 1 to 10 wt%. If the content of copper in copper-doped silica is less than 0.01 wt%, sufficient antiviral effect may not be obtained, while silica doped with copper in an amount exceeding 40 wt% may be difficult to manufacture. There is a possibility that it will be difficult. When other metals are used in combination in addition to copper, the content ratio between copper and the other metals may be, for example, 0.1 to 2 times the content of the other metals relative to the content of copper.

When the copper-doped silica is porous, the copper-doped porous silica may be, for example, the one described by the present inventors in JP-A-2020-15640. Specifically, it is as follows.

Examples of porous silica include mesoporous silica in which pores (mesopores) with a diameter of 2 to 50 nm are regularly arranged.

The specific surface area of the porous silica is preferably 500 to 2000 m ² /g, for example, from the viewpoint of maintaining durability.

Copper-doped mesoporous silica can be produced, for example, according to the following method known per se described in JP-A-2020-15640.

(Step 1)
First, a surfactant and raw materials for doping mesoporous silica with copper are dissolved in a solvent and stirred at, for example, 30 to 200° C. for 0.5 to 10 hours to form micelles in the surfactant.

The amount of surfactant dissolved in the solvent is, for example, 10 to 400 mmol/L, preferably 50 to 150 mmol/L. Alternatively, the amount of the surfactant dissolved in the solvent is, for example, 0.01 to 5.0 mol, preferably 0.05 to 1.0 mol, per 1 mol of the silica raw material added in Step 2 described below.

As the surfactant, any of cationic surfactants, anionic surfactants, and nonionic surfactants may be used, but cationic surfactants such as alkylammonium salts are preferable. . The alkylammonium salt preferably has an alkyl group having 8 or more carbon atoms, and in view of industrial ease of availability, one having an alkyl group having 12 to 18 carbon atoms is more preferable. Specific examples of alkyl ammonium salts include hexadecyltrimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, dodecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, Examples thereof include octadecyltrimethylammonium chloride, didodecyldimethylammonium bromide, ditetradecyldimethylammonium bromide, didodecyldimethylammonium chloride, and ditetradecyldimethylammonium chloride. Surfactants may be used alone or in combination of two or more.

The amount dissolved in the solvent of the raw material for doping copper into mesoporous silica (when using a combination of other metals in addition to copper, the total amount of each raw material) is based on 1 mol of the silica raw material added in step 2 described below. On the other hand, the amount is, for example, 0.001 to 1 mol, preferably 0.005 to 0.5 mol, and more preferably 0.01 to 0.1 mol.

As raw materials for doping mesoporous silica with copper or other metals in addition to copper, for example, nitrates, sulfates, chlorides, and oxychlorides of the respective metals can be used. It is preferable to use copper nitrate or copper chloride as the raw material for doping copper. In addition to copper, it is preferable to use aluminum chloride as a raw material when doping aluminum. When doping with zirconium, it is preferable to use zirconium oxychloride as the raw material. When doping with cobalt, it is preferable to use cobalt nitrate as the raw material. When doping with manganese, it is preferable to use manganese chloride as the raw material. It is preferable to use iron chloride as the raw material for doping with iron. The raw materials for doping copper and other metals in addition to copper may be used alone or in combination of two or more.

For example, water can be used as the solvent. The solvent may be a mixed solvent of water and water-soluble organic solvents including methanol, ethanol, polyhydric alcohols such as diethylene glycol, and glycerin.

(Step 2)
Next, the silica raw material is dissolved in the solution obtained in step 1 in which the surfactant forms micelles, for example at room temperature, and stirred until homogeneous to accumulate the silica raw material on the surface of the surfactant micelles. . The amount of the silica raw material dissolved in the solution is, for example, 0.2 to 1.8 mol/L. Alternatively, when water or a mixed solvent of water and a water-soluble organic solvent is used as the solvent, the amount is, for example, 0.001 to 0.05 mol per 1 mol of water.

The silica raw material is not particularly limited as long as it forms an inorganic network consisting of siloxane bonds that constitute mesoporous silica through dehydration condensation. Specific examples of the silica raw material include tetraalkoxysilanes such as tetraethoxysilane, tetramethoxysilane, and tetra-n-butoxysilane, and sodium silicate. Tetraalkoxysilane is preferred, and tetraethoxysilane is more preferred. The silica raw materials may be used alone or in combination of two or more.

(Step 3)
Next, the silica raw material accumulated on the surface of the surfactant micelles is dehydrated and condensed to form an inorganic network consisting of siloxane bonds that constitute mesoporous silica, and copper is chemically bonded and incorporated into the inorganic network. . Dehydration condensation of the silica raw material can be carried out, for example, by adding a basic aqueous solution to the system to raise the pH, and then stirring at room temperature for 1 hour or more. The basic aqueous solution is preferably added so that the pH becomes 8 to 14 immediately after addition, and more preferably 9 to 11. Specific examples of the basic aqueous solution include an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, and an aqueous ammonia solution, with an aqueous sodium hydroxide solution being preferred. The basic aqueous solution may be used alone or in combination of two or more types. Note that the dehydration condensation of the silica raw material can also be carried out by adding an acidic aqueous solution such as an aqueous hydrochloric acid solution to the system to lower the pH, and then stirring.

(Step 4)
Finally, the surfactant micelles obtained in step 3, which are composed of siloxane bonds constituting mesoporous silica and have an inorganic network in which copper is chemically bonded and incorporated, are collected by filtration as a precipitate. For example, the desired mesoporous silica doped with copper is obtained by drying at 30 to 70°C for 10 to 48 hours and then firing at 400 to 600°C for 1 to 10 hours. The mesoporous silica doped with copper thus obtained may be pulverized using a mixer or a mill, if necessary, to have a desired particle size (for example, a median diameter of 0.01 to 100 μm).

Note that the addition of the raw material for doping copper into the mesoporous silica is not limited to the mode in which it is dissolved in the solvent together with the surfactant in step 1 above, but it can also be added by dehydration condensation of the silica raw material in step 3. It may be dissolved in the solution in Step 2 or Step 3, as long as the formation of an inorganic network consisting of siloxane bonds constituting mesoporous silica is completed.

If the copper-doped silica is non-porous, the copper-doped non-porous silica can be produced using, for example, a precipitation method that is well known as a method for producing non-porous silica. . Specifically, it can be produced by allowing a raw material for doping non-porous silica with copper to coexist in the system when neutralizing an alkali metal silicate salt as a silica raw material and a mineral acid. The raw material for doping non-porous silica with copper may be the same as the raw material for doping mesoporous silica with copper described above. The amount of raw materials used for doping non-porous silica with copper (when using a combination of other metals in addition to copper, the total amount of each raw material) is per 1 mol of alkali metal silicate as a raw material for silica. , for example, 0.001 to 0.5 mol, preferably 0.01 to 0.1 mol. The alkali metal silicate used as the silica raw material may be one commonly used for producing non-porous silica by a precipitation method. Specific examples include sodium silicate and potassium silicate, and the molar ratio of silica to alkali: SiO ₂ /M ₂ O (M is Na, K, etc.) is, for example, 0.5 to 4. The amount of alkali metal silicate dissolved in a solvent (such as water) is, for example, 0.001 to 0.05 mol per mol of the solvent. Hydrochloric acid, sulfuric acid, and nitric acid can be used as the mineral acid. Copper-doped non-porous silica is obtained as a precipitate produced by the neutralization reaction of an alkali metal silicate and mineral acid, and its filtration, washing, and drying are performed using the precipitation method. The method used for manufacturing may be followed. If necessary, it may be finally fired at a high temperature of 300° C. or higher. The specific surface area (BET specific surface area) of the non-porous silica doped with copper thus produced is, for example, 0.1 to 350 m ² /g. Similar to the copper-doped mesoporous silica described above, it may be pulverized with a mixer or a mill as necessary to obtain a desired particle size (for example, a median diameter of 0.01 to 100 μm).

In the antiviral aerosol composition of the present invention, the vinyl pyrrolidone unit-containing polymer used as the resin component may be, for example, a copolymer of vinyl pyrrolidone units and units other than vinyl pyrrolidone. In this case, in order for the copper-doped silica to exhibit excellent antiviral properties and to facilitate the formation of a coating film that is firmly retained on the surface of the article, it is necessary to use a vinylpyrrolidone unit and a material other than vinylpyrrolidone. The ratio of units (vinylpyrrolidone unit: units other than vinylpyrrolidone) is preferably 2:8 to 8:2. Specific examples of copolymers of vinylpyrrolidone units and units other than vinylpyrrolidone include copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate, copolymers of vinylpyrrolidone and methylvinylimidazolinium chloride, and copolymers of vinylpyrrolidone and methacrylate. Copolymer of acid dimethylaminopropylamide, copolymer of vinylpyrrolidone and quaternized imidazoline, vinylpyrrolidone, vinylcaprolactam and methylvinylimidazolium methyl sulfate, copolymer of vinylpyrrolidone and vinyl acetate, vinylpyrrolidone and eicosene copolymers of vinylpyrrolidone and hexadecene, copolymers of vinylpyrrolidone and styrene , and copolymers of vinylpyrrolidone, vinylcaprolactam, and dimethylaminoethyl methacrylate. Further, the polymer containing vinylpyrrolidone units may be polyvinylpyrrolidone. The weight average molecular weight of the polymer containing vinylpyrrolidone units is, for example, 5,000 to 1,500,000, preferably 6,000 to 1,000,000, more preferably 7,000 to 500,000, even more preferably is 8,000 to 100,000. If the weight-average molecular weight of the polymer containing vinylpyrrolidone units is too small and the copper-doped silica is porous, the molecules will enter the pores of the silica, resulting in a decrease in antiviral properties. On the other hand, if the pores are expected to provide properties (such as deodorizing properties), it may be difficult to achieve them, but if the weight average molecular weight is too large, the molecules may completely cover the surface of the silica. Therefore, there is a risk that the antiviral properties of silica, which are exhibited by adsorbing viruses, may be inhibited. Polymers containing vinylpyrrolidone units may be used alone or in combination of two or more.

In the antiviral aerosol composition of the present invention, the alcoholic solvent may be one commonly used as a component of an aerosol composition, and specific examples thereof include methanol, ethanol, and isopropyl alcohol. The alcoholic solvents may be used alone or in combination of two or more. When using a mixed solvent of alcoholic solvent and water, the weight ratio of alcoholic solvent to water (alcoholic solvent:water) is, for example, 1:5 to 100:1.

In the antiviral aerosol composition of the present invention, the propellant may be one commonly used as a component of an aerosol composition, and specific examples include liquefied petroleum gas, nitrogen gas, carbon dioxide, dimethyl ether, Examples include hydrofluoroolefins and hydrofluorocarbons. The propellants may be used alone or in combination of two or more.

In the antiviral aerosol composition of the present invention, the respective contents of the copper-doped silica, the polymer containing vinylpyrrolidone units, the alcoholic solvent or the mixed solvent of alcoholic solvent and water, and the propellant are, for example, as follows: The content of copper-doped silica is 0.1 to 5 wt%, the content of the polymer containing vinylpyrrolidone units is 0.1 to 5 wt%, and the content of alcohol solvent or a mixed solvent of alcohol solvent and water is 30%. ~90 wt%, the content of propellant is 5-65 wt%, preferably the content of copper-doped silica is 0.2-2 wt%, the content of polymer containing vinylpyrrolidone units is 0.2-2 wt% , the content of alcoholic solvent or a mixed solvent of alcoholic solvent and water is 45-70wt%, and the content of propellant is 25-50wt%. The antiviral aerosol composition of the present invention includes pigments, fragrances, dispersants, antifoaming agents, leveling agents, lubricants, antifungal agents, preservatives, and waxes that are commonly used as components of aerosol compositions. etc. may be blended. When these components are blended, the content of the alcoholic solvent or the mixed solvent of alcoholic solvent and water is reduced by the content of these components. Furthermore, when producing the antiviral aerosol composition of the present invention, the copper-doped silica is different from the alcoholic solvent or the mixed solvent of alcoholic solvent and water used in the antiviral aerosol composition of the present invention. It is provided as a slurry suspended in a dispersion medium, or the polymer containing vinylpyrrolidone units is provided in a solvent different from the alcoholic solvent or the mixed solvent of alcoholic solvent and water used in the antiviral aerosol composition of the present invention. When the antiviral aerosol composition of the present invention is provided as a solution dissolved in water, the antiviral aerosol composition of the present invention may contain such a dispersion medium or solvent; The content of the mixed solvent of alcoholic solvent and water is reduced.

In the antiviral aerosol composition of the present invention, the weight ratio of copper-doped silica to vinylpyrrolidone unit-containing polymer (copper-doped silica:vinylpyrrolidone unit-containing polymer) is 5: The ratio is preferably 95:25 to 75:25, more preferably 15:85 to 70:30, even more preferably 25:75 to 65:35. If the proportion of copper-doped silica is too low, it may be difficult for copper-doped silica to form a coating with excellent antiviral properties, while If the ratio of coalescence is too low, it may be difficult to form a coating film that is firmly retained on the surface of the article.

The antiviral aerosol composition of the present invention can be prepared using common methods for producing aerosol compositions, such as copper-doped silica, a polymer containing vinylpyrrolidone units, an alcoholic solvent or an alcoholic solvent. It can be produced by mixing a stock solution of a mixed solvent of water with a propellant, after adjusting the temperature as necessary so that each solvent has the desired content.

It is preferable to mix copper-doped silica, a polymer containing a vinylpyrrolidone unit, an alcoholic solvent, or a mixed solvent of an alcoholic solvent and water to prepare a stock solution by ball milling them. By ball milling copper-doped silica, a polymer containing vinylpyrrolidone units, an alcohol solvent, or a mixed solvent of alcoholic solvent and water, the copper-doped silica can be transformed into a polymer containing vinylpyrrolidone units. In an alcohol-based solvent or a mixed solvent of an alcohol-based solvent and water, in which the coalesce is uniformly dissolved, a stock solution in which the coalescence is uniformly dispersed without agglomeration is obtained. is supported in a uniformly dispersed manner without agglomeration, preventing it from falling off from the coating film.Also, despite the coexistence of copper-doped silica, the polymer containing vinylpyrrolidone units However, by acquiring high adhesion to the surface of the article, copper-doped silica can exhibit excellent antiviral properties and form a coating film that is firmly adhered to the surface of the article. becomes easier. Furthermore, it becomes easier to improve the stability of the antiviral aerosol composition of the present invention and to apply it by aerosol without causing nozzle clogging.

In a ball mill, silica doped with copper, a polymer containing vinylpyrrolidone units, an alcohol solvent, or a mixed solvent of alcohol solvent and water are placed in a processing container along with the balls (media) used in the ball mill. This can be carried out by placing the treated processing container on a ball mill stand and rotating it (the number of rotations is, for example, in the range of 15 to 2,000 rpm). The ball milling time is, for example, 1 to 50 hours, preferably 6 to 30 hours. The balls used in the ball mill (for example, alumina balls or zirconia balls with a diameter of 1 to 5 mm) are made of copper-doped silica, a polymer containing vinylpyrrolidone units, an alcoholic solvent or a mixed solvent of alcoholic solvent and water, as necessary. A slurry in which the copper-doped silica, which is another component blended in the composition, is suspended in a dispersion medium different from the alcoholic solvent or the mixed solvent of alcoholic solvent and water used in the antiviral aerosol composition of the present invention. Alternatively, the polymer containing vinylpyrrolidone units may be provided as a solution in which the polymer containing vinyl pyrrolidone units is dissolved in a solvent different from the alcoholic solvent or mixed solvent of alcoholic solvent and water used in the antiviral aerosol composition of the present invention. In this case, it is preferable to use a number that is 1 to 5 times the total weight of the dispersion medium or solvent. The alcoholic solvent or the mixed solvent of alcoholic solvent and water contained in the processing container may be part of the content in the antiviral aerosol composition of the present invention. In this case, after ball milling, the alcoholic solvent or A mixed solvent of an alcoholic solvent and water may be added in an amount equal to the content in the antiviral aerosol composition of the present invention.

The antiviral aerosol composition of the present invention can be applied to textile products, nonwoven fabric products, leather products, building materials, wood, glass , plastics, films, ceramics, paper, pulp, stationery, toys, containers, caps, spouts, spouts, etc. It can be used to impart antiviral properties to items around us. The antiviral aerosol composition of the present invention may be applied to the surface of an article by, for example, filling a spray can with the antiviral aerosol composition of the present invention and applying the aerosol onto the surface of the article. By applying the antiviral aerosol composition of the present invention to the surface of the article and drying it naturally or by heating, the copper-doped silica exhibits excellent antiviral properties and is firmly attached to the surface of the article. It is possible to form a coating film that retains its properties.

The coating film formed from the antiviral aerosol composition of the present invention has an excellent antiviral effect not only against enveloped viruses but also against non-enveloped viruses because of the copper-doped silica contained in the coating film. demonstrate. Therefore, the types of viruses targeted by its antiviral action are not limited, and include various pathogenic viruses, such as enveloped viruses such as influenza A, B, and C, parainfluenza virus, and mumps virus. (mumps virus), measles virus, human metapneumovirus, respiratory syncytial virus, Nipah virus, Hendra virus, yellow fever virus, dengue virus, Japanese encephalitis virus, West Nile virus, hepatitis B, C, and D viruses, Eastern and Western Equine encephalitis virus, rubella virus, Lassa virus, Junin virus, Machupo virus, Ganarito virus, Sabia virus, Crimean-Congo hemorrhagic fever virus, sand fly fever virus, hantavirus, Sin Nombre virus, rabies virus, Ebola virus, Marburg Viruses, bat lyssavirus, human T-cell leukemia virus, human immunodeficiency virus, human coronavirus, SARS coronavirus, SARS-CoV-2 virus (COVID-19 virus), herpes virus, varicella zoster virus, EB virus, cytomegalo Viruses such as smallpox virus, monkeypox virus, cowpox virus, morasipox virus, parapox virus, and Onyongnyong virus can be targeted. Non-enveloped viruses include rhinovirus, poliovirus, foot-and-mouth disease virus, Targets include rotavirus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis A and E viruses, human parvovirus, polyomavirus, human papillomavirus, adenovirus, and coxsackievirus.

In addition, the copper-doped silica contained in the antiviral aerosol composition of the present invention can be used at any time from the time the antiviral aerosol composition of the present invention is applied to the surface of the article until the coating film is formed. also exhibits excellent antiviral effects. At this point, the alcoholic solvent or the mixed solvent of alcoholic solvent and water contained in the antiviral aerosol composition of the present invention also exhibits an antiviral effect.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention should not be interpreted as being limited to the following description.

Production reference example 1: Production of mesoporous silica doped with copper and aluminum Hexadecyltrimethylammonium chloride as a surfactant, copper chloride as a raw material for doping copper into mesoporous silica, and aluminum for doping mesoporous silica Aluminum chloride as a raw material for silica was dissolved in water as a solvent, stirred at 100°C for 1 hour, cooled to room temperature, and then tetraethoxysilane as a silica raw material was further dissolved and stirred until homogeneous. . Next, an aqueous sodium hydroxide solution as a basic aqueous solution was added to the reaction solution so that the pH immediately after addition was 9, and the mixture was stirred at room temperature for 20 hours. The generated precipitate is collected by filtration, dried at 50°C for 24 hours, and then calcined at 570°C for 5 hours to produce the desired mesoporous silica doped with copper and aluminum as a white powder with a slight bluish tint. obtained as.

In addition, hexadecyltrimethylammonium chloride as a surfactant, copper chloride as a raw material for doping copper into mesoporous silica, aluminum chloride as a raw material for doping aluminum into mesoporous silica, and water as a solvent. The amount used was as follows per 1 mol of tetraethoxysilane as a silica raw material.
Hexadecyltrimethylammonium chloride: 0.225mol
Copper chloride: 0.0204 mol
Aluminum chloride: 0.0482 mol
Water: 125mol
Further, in order to prepare an aqueous sodium hydroxide solution as a basic aqueous solution, 0.195 mol of sodium hydroxide was used per 1 mol of tetraethoxysilane as a silica raw material.

The mesoporous silica doped with copper and aluminum obtained by the above method had a specific surface area of 1100 m ² /g and a pore diameter of about 2.5 nm (using BELSORP MAX II type manufactured by Microtrack Bell Co., Ltd. Calculated by measuring the adsorption isotherm of nitrogen gas at liquid nitrogen temperature using a multi-point method and using BJH calculation). In addition, approximately 50 mg of mesoporous silica doped with copper and aluminum was accurately weighed, dissolved in 4 mL of hydrochloric acid, and the concentrations of copper and aluminum in the hydrochloric acid solution were measured using an inductively coupled plasma emission spectrometer (Thermo Fisher Scientific). Based on the measurement results, the copper content and aluminum content in mesoporous silica doped with copper and aluminum were calculated, and the copper content was The aluminum content was 2.09 wt%, and the aluminum content was 2.00 wt%. The fact that mesoporous silica is doped with copper and aluminum was confirmed using an X-ray photoelectron spectrometer (K-Alpha Surface Analysis manufactured by Thermo Fisher Scientific, hereinafter the same) and a transmission electron microscope (JEM2010 manufactured by JEOL, the same hereinafter). did.

Production Example 1: Production of the antiviral aerosol composition of the present invention (Part 1)
(Step 1)
140 g of the copper and aluminum doped mesoporous silica obtained in Manufacturing Reference Example 1, 560 g of ethanol, and 1760 g of 5 mmφ alumina balls were placed in a 2 L Eyeboy PP wide-mouth bottle, and the mixture was placed on a ball mill stand at room temperature and heated at a rotation speed of 250 rpm. After further treatment at 450 rpm for 9 hours, the alumina balls were removed to obtain an ethanol slurry containing 20 wt % mesoporous silica doped with copper and aluminum with a median diameter of about 0.6 μm ( The median diameter was measured using a laser diffraction particle size distribution analyzer (SALD-3100 manufactured by Shimadzu Corporation) (the same applies hereinafter).
(Step 2)
In a 2L Eyeboy PP wide-mouth bottle, a copolymer powder of vinylpyrrolidone and vinyl acetate (PVP/VA S630, manufactured by Ashland, ratio of vinylpyrrolidone units to vinyl acetate units 6:4, weight average molecular weight (catalog value) 51 ,000 (the same applies hereinafter) and 490 g of ethanol, and after dissolving the powder of the copolymer of vinyl pyrrolidone and vinyl acetate in the ethanol, dope with copper and aluminum with a median diameter of about 0.6 μm obtained in step 1. 175 g of ethanol slurry containing 20 wt% mesoporous silica and 1760 g of 2 mm diameter alumina balls were placed on a ball mill stand at room temperature and processed at a rotation speed of 500 rpm for 9 hours.The alumina balls were removed and the median diameter was A coating composition was obtained in which the content of mesoporous silica doped with approximately 0.5 μm of copper and aluminum was 5 wt%, the content of a copolymer of vinyl pyrrolidone and vinyl acetate was 5 wt%, and the content of ethanol was 90 wt%. The obtained coating composition and ethanol were mixed at a weight ratio of 1:4, the content of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 1 wt %, and a copolymer of vinyl pyrrolidone and vinyl acetate was prepared. A stock solution with a content of 1 wt% and an ethanol content of 98 wt% was obtained.
(Step 3)
The stock solution obtained in step 2 and liquefied petroleum gas as a propellant (vapor pressure at 20°C: 0.29 MPa, same hereinafter) were filled into an aerosol can at a weight ratio of 6:4, and the median diameter was about 0.5 μm. The content of mesoporous silica doped with copper and aluminum is 0.6 wt%, the content of vinyl pyrrolidone and vinyl acetate copolymer is 0.6 wt%, the content of ethanol is 58.8 wt%, and the content of liquefied petroleum gas is 0.6 wt%. A 40.0 wt% antiviral aerosol composition of the present invention was obtained.

Production Example 2: Production of the antiviral aerosol composition of the present invention (Part 2)
In a 2L Eyeboy PP wide-mouth bottle, 35g of mesoporous silica doped with copper and aluminum obtained in Production Reference Example 1, 315g of ethanol, and 10wt% ethanol of vinylpyrrolidone and vinyl acetate copolymer powder (PVP/VA S630). 350 g of the solution and 1700 g of alumina balls with a diameter of 2 mm were put therein, placed on a ball mill stand at room temperature, and processed at a rotational speed of 900 rpm for 24 hours.The alumina balls were then removed and a copper and aluminum doped ball with a median diameter of about 0.5 μm was prepared. A coating composition was obtained in which the mesoporous silica content was 5 wt%, the vinyl pyrrolidone and vinyl acetate copolymer content was 5 wt%, and the ethanol content was 90 wt%. The obtained coating composition and ethanol were mixed at a weight ratio of 1:4, the content of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 1 wt %, and a copolymer of vinyl pyrrolidone and vinyl acetate was prepared. A stock solution with a content of 1 wt% and an ethanol content of 98 wt% was obtained. The obtained stock solution and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 0.6 wt. %, the content of the copolymer of vinyl pyrrolidone and vinyl acetate is 0.6 wt%, the content of ethanol is 58.8 wt%, and the content of liquefied petroleum gas is 40.0 wt%. Ta.

Production Example 3: Production of the antiviral aerosol composition of the present invention (Part 3)
(Step 1)
4.4 g of copper and aluminum doped mesoporous silica obtained in Production Reference Example 1, 83.6 g of ethanol, and 220 g of 2 mm diameter alumina balls were placed in a 250 mL Eyeboy PP wide-mouth bottle, and the mixture was placed on a ball mill stand and rotated at room temperature. After processing at several 180 rpm for 8 hours, the alumina balls were removed to obtain an ethanol slurry containing 5 wt % mesoporous silica doped with copper and aluminum and having a median diameter of about 0.5 μm.
(Step 2)
Ethanol slurry with a content of 5 wt% of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm obtained in Step 1, powder of a copolymer of vinyl pyrrolidone and vinyl acetate (PVP/VA S630), ethanol were mixed and stirred at a mass ratio of 20:1:79, the content of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 1 wt%, and the content of the copolymer of vinyl pyrrolidone and vinyl acetate was 1 wt%. A coating composition having an ethanol content of 1 wt % and an ethanol content of 98 wt % was obtained as a stock solution.
(Step 3)
The stock solution obtained in step 2 and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 0. The antiviral aerosol composition of the present invention has a vinyl pyrrolidone and vinyl acetate copolymer content of 0.6 wt%, an ethanol content of 58.8 wt%, and a liquefied petroleum gas content of 40.0 wt%. I got it.

Production Example 4: Production of the antiviral aerosol composition of the present invention (Part 4)
In Step 2 of Production Example 3, an ethanol slurry containing 5 wt% of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm obtained in Step 1, and a powder of a copolymer of vinyl pyrrolidone and vinyl acetate. (PVP/VA S630), copper- and aluminum-doped mesoporous silica with a median diameter of about 0.5 μm was prepared in the same manner as in Production Example 3 except that ethanol was mixed at a mass ratio of 40:1:159. A coating composition having a content of 1 wt %, a content of a copolymer of vinyl pyrrolidone and vinyl acetate of 0.5 wt %, and a content of ethanol of 98.5 wt % was obtained as a stock solution. The obtained stock solution and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 0.6 wt. %, the content of the copolymer of vinyl pyrrolidone and vinyl acetate is 0.3 wt%, the content of ethanol is 59.1 wt%, and the content of liquefied petroleum gas is 40.0 wt%. Ta.

Production Example 5: Production of the antiviral aerosol composition of the present invention (Part 5)
A 50 wt% aqueous solution of a copolymer of vinyl pyrrolidone and vinyl acetate (PVP/VA W735, manufactured by Ashland, ratio of vinyl pyrrolidone unit to vinyl acetate unit 7:3, weight average molecular weight (catalog value) was placed in a 2L Eyeboy PP wide-mouth bottle. ) 27,300) 70g, 455g of ethanol, 175g of ethanol slurry with a median diameter of about 0.6μm obtained in Step 1 of Production Example 1 and containing 20wt% mesoporous silica doped with copper and aluminum, 2mmφ alumina balls After processing at room temperature for 9 hours at a rotation speed of 500 rpm on a ball mill stand, the alumina balls were removed and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 5 wt. %, the content of the copolymer of vinyl pyrrolidone and vinyl acetate was 5 wt %, the content of water was 5 wt %, and the content of ethanol was 85 wt %. The obtained coating composition and ethanol were mixed at a weight ratio of 1:4, the content of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 1 wt %, and a copolymer of vinyl pyrrolidone and vinyl acetate was prepared. A stock solution containing 1 wt% of water, 1 wt% of water, and 97 wt% of ethanol was obtained. The obtained stock solution and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 0.6 wt. %, the content of the copolymer of vinyl pyrrolidone and vinyl acetate is 0.6 wt%, the content of water is 0.6 wt%, the content of ethanol is 58.2 wt%, and the content of liquefied petroleum gas is 40.0 wt%. An antiviral aerosol composition was obtained.

Production Example 6: Production of the antiviral aerosol composition of the present invention (Part 6)
Instead of a 50 wt % aqueous solution of a copolymer of vinyl pyrrolidone and vinyl acetate (PVP/VA W735), a 50 wt % ethanol solution of a copolymer of vinyl pyrrolidone and vinyl acetate (PVP/VA E535, manufactured by Ashland, vinyl pyrrolidone unit) was used. Copper- and aluminum-doped mesoporous material with a median diameter of about 0.5 μm was prepared in the same manner as in Production Example 5, except that a ratio of 5:5 and a weight average molecular weight (catalog value) of 36,700 and vinyl acetate units were used. A coating composition was obtained in which the content of silica was 5 wt%, the content of the copolymer of vinyl pyrrolidone and vinyl acetate was 5 wt%, and the content of ethanol was 90 wt%. The obtained coating composition and ethanol were mixed at a weight ratio of 1:4, the content of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 1 wt %, and a copolymer of vinyl pyrrolidone and vinyl acetate was prepared. A stock solution with a content of 1 wt% and an ethanol content of 98 wt% was obtained. The obtained stock solution and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 0.6 wt. %, the content of the copolymer of vinyl pyrrolidone and vinyl acetate is 0.6 wt%, the content of ethanol is 58.8 wt%, and the content of liquefied petroleum gas is 40.0 wt%. Ta.

Production Example 7: Production of the antiviral aerosol composition of the present invention (Part 7)
Instead of a 50 wt % aqueous solution of a copolymer of vinyl pyrrolidone and vinyl acetate (PVP/VA W735), a 50 wt % ethanol solution of a copolymer of vinyl pyrrolidone and vinyl acetate (PVP/VA E335, manufactured by Ashland, vinyl pyrrolidone unit) was used. Copper- and aluminum-doped mesoporous material with a median diameter of about 0.5 μm was prepared in the same manner as in Production Example 5, except that a ratio of 3:7 and a weight average molecular weight (catalog value) of vinyl acetate unit and vinyl acetate unit of 28,800 was used. A coating composition was obtained in which the content of silica was 5 wt%, the content of the copolymer of vinyl pyrrolidone and vinyl acetate was 5 wt%, and the content of ethanol was 90 wt%. The obtained coating composition and ethanol were mixed at a weight ratio of 1:4, the content of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 1 wt %, and a copolymer of vinyl pyrrolidone and vinyl acetate was prepared. A stock solution with a content of 1 wt% and an ethanol content of 98 wt% was obtained. The obtained stock solution and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 0.6 wt. %, the content of the copolymer of vinyl pyrrolidone and vinyl acetate is 0.6 wt%, the content of ethanol is 58.8 wt%, and the content of liquefied petroleum gas is 40.0 wt%. Ta.

Production Example 8: Production of the antiviral aerosol composition of the present invention (Part 8)
Manufactured except that polyvinylpyrrolidone powder (PVP K15, manufactured by Ashland, weight average molecular weight (catalog value) 8,000) was used instead of vinylpyrrolidone and vinyl acetate copolymer powder (PVP/VA S630). In the same manner as in Example 1, a coating composition with a median diameter of about 0.5 μm and a copper and aluminum doped mesoporous silica content of 5 wt%, a polyvinylpyrrolidone content of 5 wt%, and an ethanol content of 90 wt% was obtained. Ta. The obtained coating composition and ethanol were mixed at a weight ratio of 1:4, the content of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 1 wt %, and a copolymer of vinyl pyrrolidone and vinyl acetate was prepared. A stock solution with a content of 1 wt% and an ethanol content of 98 wt% was obtained. The obtained stock solution and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 0.6 wt. %, the content of polyvinylpyrrolidone was 0.6 wt%, the content of ethanol was 58.8 wt%, and the content of liquefied petroleum gas was 40.0 wt%.

Production Example 9: Production of the antiviral aerosol composition of the present invention (Part 9)
Manufactured except that polyvinylpyrrolidone powder (PVP K30, manufactured by Ashland, weight average molecular weight (catalog value) 60,000) was used instead of vinylpyrrolidone and vinyl acetate copolymer powder (PVP/VA S630). In the same manner as in Example 1, a coating composition with a median diameter of about 0.5 μm and a copper and aluminum doped mesoporous silica content of 5 wt%, a polyvinylpyrrolidone content of 5 wt%, and an ethanol content of 90 wt% was obtained. Ta. The obtained coating composition and ethanol were mixed at a weight ratio of 1:4, the content of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 1 wt %, and a copolymer of vinyl pyrrolidone and vinyl acetate was prepared. A stock solution with a content of 1 wt% and an ethanol content of 98 wt% was obtained. The obtained stock solution and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of mesoporous silica doped with copper and aluminum with a median diameter of about 0.5 μm was 0.6 wt. %, the content of polyvinylpyrrolidone was 0.6 wt%, the content of ethanol was 58.8 wt%, and the content of liquefied petroleum gas was 40.0 wt%.

Test Example 1: Antiviral effect of coating film formed from the antiviral aerosol composition of the present invention against enveloped viruses (1) Formation of coating film by aerosol application Antiviral aerosol composition of the present invention produced in Production Example 1 Hold the filled aerosol can horizontally and spray uniformly over the entire surface of a 10 cm x 20 cm PET film for 7 seconds from a height of 15 cm (spray amount is 1.36 g/sec), then air dry. In this way, a coating film was formed on the surface of the PET film. When the antiviral aerosol composition of the present invention produced in Production Example 1 was sprayed from an aerosol can, no spray failure due to nozzle clogging was observed. The coating film formed on the surface of the PET film was white, and the supported amount of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was 0.27 mg/cm ² . The amount of mesoporous silica supported was determined by placing a PET film with a white coating on the surface in a crucible, adding 6 mol/L hydrochloric acid, heating at 120°C for 1 hour, and then using an inductively coupled plasma emission spectrometer. Calculated based on the amount of copper in the crucible measured using
(2) Evaluation of antiviral effect MDCK cells (canine kidney-derived cells) as host cells were infected with influenza A virus (H3N2, A/Hong Kong/8/68; TC adapted, ATCC VR-1679), After culturing, cell debris was removed by centrifugation to obtain a virus suspension (infectious titer: 4.7×10 ⁷ PFU/mL). 0.4 mL of this virus suspension was dropped onto a 5 cm square test piece cut from a PET film with a white coating formed on the surface according to ISO 21702, covered with a 4 cm square cover film, and then heated at 25°C. I left it there. After 24 hours, a virus washing solution was added to the test piece to wash out the virus, and the virus infectivity titer was measured by plaque measurement. The results are shown in Table 1. In addition, Table 1 shows the results of similar tests using the antiviral aerosol compositions of the present invention produced in Production Examples 5 to 7, and as a control, a virus suspension was dropped onto a 5 cm square PET film. The results are also shown.

As is clear from Table 1, the coating films formed from the antiviral aerosol compositions of the present invention produced in Production Examples 1 and 5 to 7 have excellent antiviral effects against influenza viruses, which are enveloped viruses. demonstrated.

Test Example 2: Antiviral effect of the coating film formed from the antiviral aerosol composition of the present invention against non-enveloped viruses (1) Formation of coating film by aerosol application Antiviral aerosol of the present invention produced in Production Example 1 A white coating film was formed from the composition on the surface of a 10 cm x 20 cm PET film in the same manner as in Test Example 1.
(2) Evaluation of antiviral effect Feline calicivirus (F-9, Feline calicivirus ; Strain: F-9, ATCC VR-782) as a norovirus alternative virus was added to CRFK cells (feline kidney-derived cells) as host cells. After culturing, cell debris was removed by centrifugation to obtain a virus suspension (infectious titer: 2.4 x 10 ⁷ PFU/mL). 0.4 mL of this virus suspension was dropped onto a 5 cm square test piece cut from a PET film with a white coating formed on the surface according to ISO 21702, covered with a 4 cm square cover film, and then heated at 25°C. I left it there. After 24 hours, a virus washing solution was added to the test piece to wash out the virus, and the virus infectivity titer was measured by plaque measurement. The results are shown in Table 2. In addition, Table 2 shows the results of similar tests using the antiviral aerosol compositions of the present invention produced in Production Examples 5 to 7, and as a control, a virus suspension was dropped onto a 5 cm square PET film. The results are also shown.

As is clear from Table 2, the coating films formed from the antiviral aerosol compositions of the present invention produced in Production Examples 1 and 5 to 7 had excellent resistance against feline calicivirus, which is a non-enveloped virus. exerted a viral effect.

Test Example 3: Adsorption effect of a coating film formed from the antiviral aerosol composition of the present invention on hemagglutinin (HA) A coating film formed from the antiviral aerosol composition of the present invention on HA, a surface protein of influenza virus The adsorption effect of the membrane was measured using HA (H1N1) (A/California/06/2009 Hemagglutinin ELISA Development Kit (Immune Technology IT-E3Ag-2009H1N1-California/06). Specifically, Production Example 1 A test piece with an area of 7.4 cm ² (median A piece of mesoporous silica doped with copper and aluminum (with a diameter of about 0.5 μm and a supported amount of 2 mg) was cut out, immersed in 2 mL of an HA solution with an initial concentration of 25.3 ng/mL, and stirred for 20 seconds using a vortex mixer. After 3 minutes, the film was removed and centrifuged to precipitate the solid content. The supernatant was collected and the concentration of HA was measured. Adsorption rate (%) = ((HA The adsorption rate for HA was calculated from the formula: initial concentration - HA concentration after 3 minutes)/initial HA concentration) x 100. 2 mg of mesoporous silica doped with copper and aluminum having a median diameter of about 0.5 μm was added, and the adsorption rate of mesoporous silica to HA was calculated in the same manner as 100. Relative values are shown in Table 3. Also shown are the results of similar tests conducted using the antiviral aerosol compositions of the present invention produced in Production Examples 8 and 9.

As is clear from Table 3, the adsorption rate for HA of the coating film formed from the antiviral aerosol composition of the present invention produced in Production Example 1 was as follows: The adsorption rate of mesoporous silica for HA was almost the same as that of mesoporous silica, and there was almost no decrease in the adsorption rate of mesoporous silica for HA due to coexistence with the copolymer of vinyl pyrrolidone and vinyl acetate in the coating film. It was confirmed that the coating film formed from the antiviral aerosol composition of the present invention produced in Production Example 1 had an excellent adsorption effect on HA. It was also possible to confirm that the coating film formed from the antiviral aerosol composition of the present invention produced in Production Examples 8 and 9 had an excellent adsorption effect on HA, but it decreased as the weight average molecular weight of polyvinylpyrrolidone increased. It was inferred that there is a tendency to

Test Example 4: Durability of coating film formed from the antiviral aerosol composition of the present invention The aerosol can filled with the antiviral aerosol composition of the present invention produced in Production Example 1 was held horizontally and placed at a distance of 15 cm. From a height of and test piece B) were cut out. Cellotape (registered trademark, hereinafter the same) was firmly attached to the entire surface of the coating film of test specimen A by pressing it with the hand, and then immediately peeled off. After removing the cellophane tape, test pieces A and B were placed in a crucible, 6 mol/L hydrochloric acid was added, and heated at 120°C for 1 hour, and the amount of copper in the crucible was determined by inductively coupled plasma emission spectrometry. By measuring using a device, the amount of copper in each of test piece A and test piece B after peeling off the sellotape is determined, and the coating film remaining rate (%) = (of test piece A after peeling off the sellotape) The durability of the coating film was evaluated using the formula: amount of copper/amount of copper in test piece B)×100. The results are shown in Table 4. Table 4 shows the results of similar tests using the antiviral aerosol compositions of the present invention produced in Production Examples 4 and 5, as well as the results of tests using copper and aluminum with a median diameter of about 0.5 μm as controls. Results of a similar test in which an aerosol can was filled with a stock solution containing 1 wt% of doped mesoporous silica and 99 wt% of ethanol and liquefied petroleum gas as a propellant at a weight ratio of 6:4. Also shown.

As is clear from Table 4, by using a polymer containing vinylpyrrolidone units as the resin component of the aerosol composition, a coating film that was firmly retained on the surface of the PET film could be formed by aerosol application. .

Test Example 5: Spray adhesion of the antiviral aerosol composition of the present invention When the aerosol composition is sprayed onto the surface of an object, a portion of the stock solution is blown up from the surface of the object by a strong air current and does not adhere. Since a scattering phenomenon occurs, the spray adhesion of the aerosol composition should be evaluated using the formula: spray adhesion rate (%) = (actual application amount of undiluted solution per unit area/theoretical application amount of undiluted solution per unit area) x 100. I can do it. Here, the actual amount of undiluted solution applied per unit area is calculated by dividing the amount of deposits on the surface of the object immediately after spraying the aerosol composition by the applied area, and the theoretical amount of undiluted solution applied per unit area is Calculated by dividing the theoretical coating amount by the coating area. The theoretical application amount of the stock solution is calculated from the formula: (Amount of aerosol composition before injection - Amount of aerosol composition after injection) x Ratio of stock solution of the aerosol composition. The spray adhesion of the antiviral aerosol composition of the present invention produced in Production Example 1 when a coating film was formed in Test Example 4 was evaluated according to this method. The results are shown in Table 5. Table 5 shows the results of similar tests using the antiviral aerosol compositions of the present invention produced in Production Examples 4 and 5, and the results of tests using copper and aluminum with a median diameter of about 0.5 μm as controls. Results of a similar test in which an aerosol can was filled with a stock solution containing 1 wt% of doped mesoporous silica and 99 wt% of ethanol and liquefied petroleum gas as a propellant at a weight ratio of 6:4. Also shown.

As is clear from Table 5, by using a polymer containing a vinylpyrrolidone unit as the resin component of the aerosol composition, the spray deposition rate of the aerosol composition could be increased. Considering the results of Test Example 5 together with the results of Test Example 4, the antiviral aerosol composition of the present invention can form a coating film that is firmly retained on the surface of a PET film with a high spray adhesion rate by aerosol application. It turns out that it is possible to form.

Test Example 6: Stability of the antiviral aerosol composition of the present invention 20 g of each of the antiviral aerosol compositions of the present invention produced in Production Examples 1 to 9 were filled into 100 mL pressure-resistant glass bottles, and the appearance was observed. When the following five items were investigated, it was found that none of the antiviral aerosol compositions of the present invention had any practically problematic phenomena in any of the items, and had high stability.
- Are the components of the stock solution other than mesoporous silica compatible with the liquefied petroleum gas? - Is there any precipitate formation? - Is there any discoloration of the composition due to the elution of copper or aluminum? - Shake the precipitated mesoporous silica. Is there any aggregation of mesoporous silica? The composition of the antiviral aerosol composition of the present invention manufactured in Production Example 1 was changed, and the content of mesoporous silica was increased to 3 wt%. The content of vinyl pyrrolidone and vinyl acetate copolymer was increased to 3 wt% (reducing the ethanol content by the same amount), or the ethanol content was reduced to 40 wt% (reducing the ethanol content by the same amount). (increase the content of liquefied petroleum gas by the same amount), increase the content of ethanol to 90 wt% (reduce the content of liquefied petroleum gas by the increased amount), reduce the content of liquefied petroleum gas to 10 wt% (by the reduced amount) increase the content of ethanol), increase the content of liquefied petroleum gas to 60 wt% (reduce the content of ethanol by the increased amount), change the liquefied petroleum gas to hydrofluoroolefins (e.g. HFO-1234ze), Although nitrogen gas and carbon dioxide gas were mixed with petroleum gas, there was no significant difference in stability evaluation. Furthermore, even when ethanol (58.8 wt%) was changed to ethanol (10.8 wt%) + water (48.0 wt%) and liquefied petroleum gas was changed to dimethyl ether, there was no significant difference in stability evaluation. . The same composition changes as those made to the antiviral aerosol composition of the present invention produced in Production Example 1 were made to the antiviral aerosol composition of the present invention produced in Production Example 9. There was no significant difference in stability evaluation.
However, the copolymer of vinyl pyrrolidone and vinyl acetate in the antiviral aerosol composition of the present invention produced in Production Example 1 was replaced with ethylcellulose (Antaron ECo ethylcellulose, manufactured by Ashland), which is known as the resin component of the aerosol composition. ), (octylacrylamide/hydroxypropyl acrylate/butylaminoethyl methacrylate) copolymer (AMPHOMER, manufactured by Nouryon), polyglyceryl-3 dimer dilinoleic acid diisostearate, tri(caprylic acid/capric acid) glyceryl (SolAmaze, manufactured by Nouryon) When the above five items were examined for aerosol compositions manufactured by changing to either LIPIDURE-PMB or Polyquaternium-51 (LIPIDURE-PMB, manufactured by NOF Corporation), it was found that all aerosol compositions contained at least one Phenomena that caused practical problems were observed in some items, and it was found that the stability was poor.

Production reference example 2: Production of non-porous silica doped with copper and aluminum Sodium silicate (sodium metasilicate (nase hydrate) as a silica raw material: manufactured by Nihon Kagaku Kogyo Co., Ltd., SiO ₂ /Na ₂ O = 0. 9 to 1.1 (manufacturer's value)) in water as a solvent, and dope non-porous silica with copper chloride and aluminum as raw materials for doping copper into non-porous silica. A solution (b) was prepared by dissolving aluminum chloride as a raw material in water as a solvent. Solution (a) and solution (b) were mixed at room temperature, stirred for 5 minutes, and then hydrochloric acid was added dropwise over 30 minutes while stirring (the pH at the start of hydrochloric acid addition was 14 and the pH at the end was 9). ). After about 30 minutes, the generated precipitate was suction filtered, and the filtered precipitate was thoroughly washed with water (until the electrical conductivity of the washing liquid was less than 1000 μS), and then dried at 80° C. overnight. The collected filter cake was roughly pulverized with a mixer and then calcined at 570°C for 5 hours to obtain the desired non-porous silica doped with copper and aluminum as a white powder with a slight bluish tint.

The amounts of copper chloride used as a raw material for doping non-porous silica with copper, aluminum chloride as a raw material for doping aluminum into non-porous silica, and water as a solvent are as follows: It was as follows with respect to 1 mol of sodium silicate.
Copper chloride: 0.0201 mol
Aluminum chloride: 0.0475 mol
Water for preparing solution (a): 48.6 mol
Water for preparing solution (b): 90.2 mol
Further, 1.59 mol of hydrochloric acid was used per 1 mol of sodium silicate as a silica raw material.

The non-porous silica doped with copper and aluminum obtained by the above method had a BET specific surface area of 18.8 m ² /g. Further, the content of copper in the non-porous silica doped with copper and aluminum was 1.43 wt%, and the content of aluminum was 2.03 wt%. It was confirmed using an X-ray photoelectron spectrometer and a transmission electron microscope that the non-porous silica was doped with copper and aluminum.

Production Example 10: Production of the antiviral aerosol composition of the present invention (Part 10)
In the same manner as Production Example 1, except that instead of the mesoporous silica doped with copper and aluminum obtained in Production Reference Example 1, the non-porous silica doped with copper and aluminum obtained in Production Reference Example 2 was used. , a coating composition with a content of 5 wt% of non-porous silica doped with copper and aluminum with a median diameter of about 0.5 μm, a content of a copolymer of vinyl pyrrolidone and vinyl acetate of 5 wt%, and a content of ethanol of 90 wt%. I got something. The obtained coating composition and ethanol were mixed at a weight ratio of 1:4, the content of non-porous silica doped with copper and aluminum was 1 wt%, the content of the copolymer of vinyl pyrrolidone and vinyl acetate was 1 wt%, A stock solution with an ethanol content of 98 wt% was obtained. The obtained stock solution and liquefied petroleum gas as a propellant were filled into an aerosol can at a weight ratio of 6:4, and the content of non-porous silica doped with copper and aluminum was 0.6 wt%, vinylpyrrolidone and acetic acid. An antiviral aerosol composition of the present invention was obtained, containing a vinyl copolymer content of 0.6 wt%, an ethanol content of 58.8 wt%, and a liquefied petroleum gas content of 40.0 wt%. This antiviral aerosol composition of the present invention had the same spray adhesion and stability as the antiviral aerosol composition of the present invention produced in Production Example 1. Furthermore, the coating film formed from the antiviral aerosol composition of the present invention has antiviral action and durability equivalent to that of the coating film formed from the antiviral aerosol composition of the present invention produced in Production Example 1. It had a

The present invention provides copper-doped silica that exhibits excellent antiviral properties and is highly stable, capable of forming a coating film that is firmly retained on the surface of articles, and that prevents nozzle clogging. It is an industry-leading invention in that it is possible to provide an antiviral aerosol composition that can be applied by aerosol without causing any damage, a coating film formed from the antiviral aerosol composition, and an article having the coating film. With availability above.

Claims (11)

(1) Silica doped with copper; (2) a copolymer of vinylpyrrolidone and vinyl acetate as a polymer containing vinylpyrrolidone units (ratio of vinylpyrrolidone to vinylacetate is 2:8 to 8:2); and At least one member selected from the group consisting of polyvinylpyrrolidone
(3) An antiviral aerosol composition comprising an alcoholic solvent or a mixed solvent of an alcoholic solvent and water; and (4) a propellant. The antiviral aerosol composition according to claim 1, wherein the silica is further doped with aluminum. The antiviral aerosol composition according to claim 1, wherein the silica is porous silica. The antiviral aerosol composition according to claim 1, wherein the weight average molecular weight of the polymer containing pyrrolidone units is 5,000 to 1,500,000. The antiviral aerosol composition according to claim 1, wherein the alcohol solvent is ethanol. The antiviral aerosol composition according to claim 1, wherein the propellant is at least one selected from the group consisting of liquefied petroleum gas, nitrogen gas, carbon dioxide, dimethyl ether, hydrofluoroolefins, and hydrofluorocarbons. In the antiviral aerosol composition, the respective contents of the copper-doped silica, the polymer containing vinylpyrrolidone units, the alcoholic solvent or the mixed solvent of alcoholic solvent and water, and the propellant are doped with copper. The content of silica is 0.1 to 5 wt%, the content of the polymer containing vinylpyrrolidone units is 0.1 to 5 wt%, the content of alcohol solvent or a mixed solvent of alcohol solvent and water is 30 to 90 wt%, injection The antiviral aerosol composition according to claim 1, wherein the content of the agent is 5 to 65 wt%. Claim 1, wherein the weight ratio of the copper-doped silica to the vinylpyrrolidone unit-containing polymer (copper-doped silica:vinylpyrrolidone unit-containing polymer) is from 5:95 to 75:25. antiviral aerosol composition. (1) Silica doped with copper; (2) a copolymer of vinylpyrrolidone and vinyl acetate as a polymer containing vinylpyrrolidone units (ratio of vinylpyrrolidone to vinylacetate is 2:8 to 8:2); and At least one member selected from the group consisting of polyvinylpyrrolidone
(3) A step of mixing an alcohol-based solvent or a mixed solvent of an alcohol-based solvent and water in a processing container and a step of ball milling the stock solution obtained by the preparation method with (4) a propellant. A method for producing an antiviral aerosol composition. A coating film formed from the antiviral aerosol composition according to claim 1. An article comprising the coating film according to claim 10 .